Via a novel mechanical cleavage technology, TiNbO5− (TNN) nanosheets are obtained from the corresponding layered compound. X-ray diffraction pattern is employed to determine the phase transformation of the specimens during the whole process, and the microstructure of the samples is analyzed by scanning electron microscope, transmission electron microscope, and atomic force microscope. The results indicate that the compression and shearing of the designed rolling machine play an important role in the crack and the exfoliation of the aggregated layered compound. Subsequently, the TNN nanosheets with the 0.91 nm thickness have been successfully fabricated with the assist of microwave and ultrasonic technique. With the layer by layer technique, (Polyetherimide/TNN)n films are deposited on the substrate with glass. It is found that the multilayer film with ten cycles treated at 450 °C exhibited photo-induced hydrophilicity under ultraviolet irradiation and high photocatalytic oxidation activity. The outstanding self-cleaning ability of the TNN nanosheets coated glass can be seen from the appearance photograph by naked eyes.Graphical Abstract: